AU2020325766B2

AU2020325766B2 - Fungicide composition

Info

Publication number: AU2020325766B2
Application number: AU2020325766A
Authority: AU
Inventors: Marco Bernardini; Francesca Borgo; Cristina RAPETTI; Gianluca Valieri
Original assignee: Sipcam Oxon SpA
Current assignee: Sipcam Oxon SpA
Priority date: 2019-08-08
Filing date: 2020-08-05
Publication date: 2026-01-22
Anticipated expiration: 2040-08-05
Also published as: KR20220041922A; BR112022002379A2; CL2022000306A1; ZA202201556B; CN114501994B; MX2022001630A; WO2021024189A1; EP4009787A1; AU2020325766A1; IT201900014445A1; KR102924329B1; US20220330545A1; PH12022550264A1; CN114501994A; CA3146460A1

Abstract

The present invention refers to an aqueous composition comprising prothioconazole, optionally chlorothalonil, and at least one sulfonate surfactant, said composition having a pH <7. The present invention also refers to a production process of said composition, and to the use of the composition in the treatment and/or the prevention of fungal infections in plants.

Description

TRANSLATION (Rule 12.3) 31 AUGUST 2020 wo 2021/024189 WO PCT/IB2020/057377

"FUNGICIDE COMPOSITION" *

Technical field

The invention refers to the field of fungicide compositions. In particular, the present

5 invention refers to chemically and physically stable water-based compositions with

fungicide activity, and to a process for the production of such compositions.

Technical background

Several compounds with fungicide activity are known.

Such compounds are generally used in compositions adapted to be used in the

10 agricultural field, to prevent and/or treat fungal infections in plants.

Among the fungicide compositions, compositions comprising prothioconazole are

known.

However, it is known that the compositions comprising prothioconazole, in particular

the water-based liquid compositions, have stability problems. For example, the Patent

15 Application CA3007969A1 describes that, during storage, in particular in presence of

conditions such as high temperatures, incident light and oxygen contact,

prothioconazole can undergo degradation, thus generating 2-(1-cyclopropyl)-1-(2-

chloropheny1)-3-(1H-1,2,4-triazol-1-y1)propan-2-ol. In consequence, the amount of

prothioconazole, i.e. of the fungicide active ingredient, in the formulation is reduced.

20 CA3007969A1 deals with the problem of providing formulations containing

prothioconazole, which have high stability during storage and which do not show any

significant degradation of prothioconazole to 2-(1-chlorocyclopropy1)-1-(2-

chloropheny1)-3-(1H-1,2,4-triazol-1-y1)propan-2-o1. In CA3007969A1, such problem

is solved by providing liquid formulations comprising prothioconazole and at least one

25 organic solvent, e.g., N,N-dimethyl 9-decenamide (CAS number 1356964-77-6).

However, solvent-based formulates have several disadvantages such as, e.g., high

environmental impact, poor handling of the formulated product, both in terms of risk

increase for the production operators and for the final user, and the possible

toxicological classification of the solvents used as dangerous compounds which could

30 reflect also upon the classification of the formulated product itself.

Fungicide compositions comprising more than one active ingredient, e.g.

WO wo 2021/024189 PCT/IB2020/057377

prothioconazole and chlorothalonil, are known.

The International Application WO2018/210158A1 describes a fungicide composition

comprising prothioconazole and chlorothalonil. WO2018/210158A1 deals with the

problem of phytotoxicity of such compounds, in particular of chlorothalonil, and

teaches that by combining chlorothalonil with prothioconazole a reduction of the

phytotoxic effects of both compounds is achieved. WO2018/210158A1 also describes

that the combination of prothioconazole and chlorothalonil produces a synergic

enhancement of the fungicide activity which, in the combination, is higher than

expected by the sum of the activity of the two single compounds.

However, the combination of prothioconazole with other active ingredients does not

allow to overcome the instability problem of the composition, in particular of the

tendency of prothioconazole to undergo degradation.

There exists therefore the need of providing fungicide compositions, in particular

water-based compositions, which are effective and which have both chemical and

physical high stability.

Summary of the invention

Aim of the present invention is to solve the above discussed problems and to provide

a composition having high fungicide activity.

Further aim of the present invention is to provide a composition with fungicide activity

which is stable, in particular both chemically stable and physically stable.

Still other aim of the present invention is to provide a fungicide composition having a

production process which is easily feasible, also at industrial level, and which allows

a good production yield.

These and other aims are achieved by an aqueous composition according to claim 1.

The present invention also refers to a production process of such composition,

according to claim 15, and to its use in the treatment and/or the prevention of fungal

infections in plants, according to claim 18.

Preferred aspects of the present invention are object of the dependent claims 2-14 and

16-17.

Detailed description

In the following description, the characteristics of the invention will be described

WO wo 2021/024189 PCT/IB2020/057377

referring to exemplary embodiments; however, each of the characteristics herein

described can be combined with one or more other characteristics herein described,

providing further embodiments of the present invention. Such embodiments must be

considered described by the present description.

As mentioned above, an object of the present invention is an aqueous composition

comprising prothioconazole, and at least one sulfonate surfactant, said composition

having pH <7.

Advantageously, the composition of the present invention results to be stable over

time, both physically and chemically, keeping high fungicide activity.

Indeed, it has been surprisingly observed that an aqueous composition comprising

prothioconazole and at least one sulfonate surfactant, having a pH <7, results to be

both physically and chemically stable.

In particular, the composition of the present invention is, advantageously, physically

stable, i.e. it maintains substantially unaltered over time the physical characteristics

allowing its final use such as, e.g., fluidity, lack of phase separation and lack of

sediments.

Moreover, the composition of the present invention is, advantageously, chemically

stable, i.e. it does not have a degradation level over time of the active ingredients

contained therein (in particular of prothioconazole), such that the antifungal effect of

the composition results to be substantially altered or compromised.

Prothioconazole, having IUPAC name 12-[2-(1-chorocyclopropyl)-3-(2-chlorophenyl)-

2-hydroxypropy1]-2,4-dihydro-1,2,4-triazole-3-thione, is a synthetic compound, per se

known, of the triazole class. Prothioconazole is a systemic fungicide, which can be

absorbed by the plant, e.g. by the roots and/or the leaves, and be then distributed within

the plant.

Optionally, the composition according to the present invention can include at least a

second compound with antifungal activity, chlorothalonil.

Chlorothalonil, having IUPAC name tetrachloroisophthalonitrile, belongs to the class

of chloronitriles. Chlorothalonil is a non-systemic fungicide, i.e. it is not absorbed by

the plant but it acts on the fungi which are located on the plant surface.

In embodiments, the aqueous composition of the invention has pH <7 and comprises

WO wo 2021/024189 PCT/IB2020/057377

prothioconazole, chlorothalonil, and at least one sulfonate surfactant.

In embodiments, the composition has pH <5, preferably <3.5, more preferably between

2 and 3.5. Preferably the pH of the composition remains substantially constant over

time, i.e. a pH variation remains within one pH unit, preferably 0.5 pH units. For

example, an initial pH of 2.0 will not exceed the value of 3.0 (or will not fall below

1.0), preferably it will not rise above 2.5 (or will fall below 1.5).

In embodiments, the composition can have pH <3.

In embodiments, the composition of the invention can comprise at least one acid

selected from inorganic acids, organic acids and mixtures thereof.

In other words, in embodiments, the composition can comprise prothioconazole,

optionally chlorothalonil, one or more sulfonate surfactants and one or more acids.

The acids which can be used in the composition of the invention can be one or more

inorganic acids, one or more organic acids, or a combination of one or more inorganic

acids and one or more organic acids.

Advantageously, when the composition of the invention comprises one or more acids,

the composition results to be particularly stable, both physically and chemically, even

for long periods.

In embodiments, when the composition comprises one or more acids, the pH of the

composition is preferably <3.5, more preferably between 2 and 3.5. In embodiments,

the composition can have pH <3.

Moreover, it has been surprisingly observed that, advantageously, when the

composition comprises one or more acids, the pH of the composition remains

substantially constant over time, even for long periods.

In embodiments, one or more inorganic acids, which can be used in the composition

of the invention, can be selected from sulfuric acid, phosphoric acid, hydrochloric acid,

hydrobromic acid, hydroiodic acid, hydrofluoric acid, hydroastatic acid, hydrogen

sulfide, hydrogen selenide, hydrogen telluride, hydrazoic acid, hydrogen cyanide,

boric acid, carbonic acid, nitrous acid, nitric acid, hypophosphorous acid, phosphorous

acid, pyrophosphoric acid, sulfurous acid, hypochlorous acid, chlorous acid, chloric

acid, perchloric acid, iodic acid and mixtures thereof.

In embodiments, the composition of the invention can comprise one or more acids

WO wo 2021/024189 PCT/IB2020/057377

selected from sulfuric acid, phosphoric acid, hydrochloric acid, and mixtures thereof.

In embodiments, one or more organic acid, which can be used in the composition of

the invention, can be selected from carboxylic acids, peroxyacids, sulfonic acids,

sulfinic acids, sulfenic acids, phosphonic acids and mixtures thereof. For example, one

or more organic acids can be selected from citric acid, acrylic acid, adipic acid, aldaric

acid, oxalic acid, phthalic acid, azelaic acid, sebacic acid, isocitric acid, butyric acid,

oleic acid, palmitic acid, stearic acid, glutamic acid, aspartic acid, acetoacetic acid,

pyruvic acid, levulinic acid, benzoic acid, salicylic acid, cinnamic acid, caffeic acid,

glycolic acid, lactic acid, salicylic acid, gentisic acid and mixtures thereof. In an

embodiment, the composition of the invention comprises citric acid.

In embodiments, the composition of the invention comprises prothioconazole,

optionally chlorothalonil, at least one sulfonate surfactant, and at least one acid

selected from sulfuric acid, phosphoric acid, hydrochloric acid, citric acid and mixtures

thereof.

As mentioned above, the composition of the invention includes at least one sulfonate

surfactant. In embodiments, the composition includes a plurality of sulfonate

surfactants.

Sulfonate surfactants, which can be used in the composition of the invention, are, per

se known in the art and commercially available.

In embodiments, one or more sulfonate surfactants, which can be used in the

composition of the invention, can be selected from alkylsulfonates, alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates,

sulfonates of fatty acids, sulfonates of alkylphenols, sulfonates of alkoxylated

arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and

tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates,

sulfosuccinamates and mixtures thereof.

In embodiments, the composition of the invention can comprise one or more sulfonate

surfactants selected from alkylnaphthalenesulfonates, lignosulfonates and mixtures

thereof.

surfactants selected from alkylnaphthalenesulfonates, lignosulfonates,

alkylarylsulfonates and mixtures thereof.

In embodiments, the composition of the invention includes at least one

alkylnaphthalenesulfonate surfactant and at least one lignosulfonate surfactant,

preferably at least one methylnaphthalenesulfonate surfactant and at least one

lignosulfonate surfactant.

In embodiments, the composition of the invention includes at least one

alkylnaphthalenesulfonate surfactant, at least one lignosulfonate surfactant, and at

least one alkylarylsulfonate surfactant.

For example, in embodiments, the composition of the invention can comprise

prothioconazole, optionally chlorothalonil, one methylnaphthalenesulfonate

surfactant, one lignosulfonate surfactant, and optionally one or more acids, e.g. sulfuric

acid and/or phosphoric acid and/or hydrochloric acid and/or citric acid.

In embodiments, the composition of the invention can further comprise at least one

non-sulfonate surfactant.

In embodiments, the amount by weight of prothioconazole is between 1% and 50%,

preferably between 2% and 45%, more preferably between 2% and 40%, relative to

the total weight of the composition.

In embodiments, the amount by weight of prothioconazole is between 1% and 50%,

preferably between 2% and 30%, more preferably between 2% and 20%, relative to

the total weight of the composition.

When the composition of the invention comprises chlorothalonil, the amount by

weight of chlorothalonil is preferably between 1% and 55%, more preferably between

10% and 55%, still more preferably between 20% and 55% relative to the total weight

of the composition.

According to an aspect, the composition of the invention comprises at least one

sulfonate surfactant. In embodiments, the amount by weight of said at least one

sulfonate surfactant is preferably between 0.5% and 25%, more preferably between

2% and 15%, still more preferably between 4% and 10%, relative to the total weight

of the composition.

wo 2021/024189 WO PCT/IB2020/057377

When the composition of the invention comprises a plurality of sulfonate surfactants,

the total amount by weight of sulfonate surfactants is preferably between 0.5% and

25%, more preferably between 2% and 15%, still more preferably between 4% and

10%, relative to the total weight of the composition.

In embodiments, in the composition according to the invention, the concentration of

said prothioconazole can be in the range between 10 g/l and 600 g/l, preferably

between 20 g/l and 500 g/l, more preferably between 30 g/l and 450 g/l. In

embodiments, the concentration of prothioconazole can be about 400 g/l.

said prothioconazole can be in the range between 10 g/l and 500 g/l, preferably

between 20 g/l and 250 g/l, more preferably between 30 g/l and 200 g/l.

In embodiments, the concentration of prothioconazole can be, e.g., in the range

between 50 g/l and 300 g/l, in the range between 75 g/l and 200 g/l or in the range

between 100 g/l and 200 g/l.

In other embodiments, the concentration of prothioconazole can be, e.g., in the range

between 10 g/l and 100 g/l, in the range between 20 g/l and 80 g/l or in the range

between 30 g/l and 60 g/l.

In embodiments, when the composition according to the present invention includes

chlorothalonil, the concentration of chlorothalonil can be in the range between 100 g/l

and 700 g/l, preferably between 200 g/l and 700 g/l, more preferably between 300 g/l

and 700 g/l.

In embodiments, the concentration of chlorothalonil can be, e.g., in the range between

200 g/l and 600 g/l, in the range between 250 g/l and 500 g/l or in the range between

300 g/l and 400 g/l.

In other embodiments, the concentration of chlorothalonil can be, e.g., in the range

between 300 g/l and 700 g/l, in the range between 400 g/l and 700 g/l or in the range

between 500 g/l and 700 g/l.

For example, the composition of the invention can comprise prothioconazole in a

concentration in the range between 100 g/l and 200 g/l and chlorothalonil in a

concentration in the range between 300 g/l and 400 g/l.

For example, the composition of the invention can comprise prothioconazole in a

concentration in the range between 30 g/l and 60 g/l and chlorothalonil in a

concentration in the range between 500 g/l and 700 g/l.

According to an aspect, the composition of the invention is an aqueous composition.

In embodiments, the composition is an aqueous suspension, preferably an aqueous

suspension concentrate (SC). The above stated percentages refer to a concentrated

aqueous composition; the suspension concentrate is typically diluted at the moment of

use.

In agricultural field the use of compositions containing one or more active ingredients,

in form of aqueous suspensions, in particular of aqueous suspension concentrates (SC),

is per se known.

In general, the aqueous suspensions are liquid formulations wherein the active

ingredient (or the active ingredients) is suspended in water, optionally micronized (e.g.

in the form of particles having size between 1 um and 6 um). Optionally, the aqueous

suspensions can further include one or more components selected from surfactants,

dispersants, antifreezes, defoamers, antibacterials and/or anti-molds (i.e. biocides),

and thickeners.

In embodiments, the composition according to the present invention can comprise one

or more antifreezes, and/or one or more dispersants, and/or one or more defoamers,

and/or one or more biocide agents, and/or one or more thickeners.

Antifreezes which can be used in the composition of the invention are per se known

and commercially available. For example, antifreezes which can be used in the

composition of the invention are glycols, e.g. monopropylene glycol (MPG).

Dispersants which can be used in the composition of the invention are per se known

and commercially available. For example, dispersants which can be used in the

composition of the invention are alkylnaphthalenesulfonates and lignosulfonates.

Defoamers which can be used in the composition of the invention are per se known

and commercially available. For example, defoamers which can be used in the

composition of the invention are silicone defoamers.

Biocide agents, e.g. antibacterials and anti-molds, which can be used in the

composition of the invention, are per se known and commercially available. In general, biocide agents can be added to the aqueous compositions comprising active ingredients, for agricultural use, in order to prevent the contamination of such compositions from bacteria and/or molds. For example, biocides which can be used in the composition of the invention are the compounds belonging to the class of benzisothiazolinones.

Thickeners which can be used in the composition of the invention are per se known

and commercially available. For example, thickeners which can be used in the

composition of the invention are natural gums, such as for example xanthan gum, guar

gum, acacia gum (or gum arabic), gum karaya, tara gum, gellan gum and mixtures

10 thereof.

In embodiments, the composition of the invention can further comprise one or more

non-sulfonate surfactants. In other words, in embodiments the composition can

comprise, in addition to at least one sulfonate surfactant, one or more non-sulfonate

surfactants, i.e. which do not belong to the class of sulfonate surfactants.

The composition of the present invention can be prepared by means of a process

comprising a step of mixing prothioconazole, optionally chlorothalonil, and at least

one sulfonate surfactant, in water.

Further object of the present invention is a process for the preparation of the

composition of the invention, such process comprising a step of mixing

prothioconazole, optionally chlorothalonil, and at least one sulfonate surfactant, in

water.

According to an aspect, the composition has pH <7, preferably has pH <5, more

preferably has pH <3.5, and still more preferably has pH between 2 and 3.5.

In embodiments, the composition can have pH <3.

According to embodiments, the process according to the present invention comprises

a step of adding at least one acid selected from inorganic acids, organic acids and

mixtures thereof. In this case, advantageously, it is possible to regulate the pH of the

composition to a specific value, which can be optionally preselected. Moreover, as

discussed above, it has been surprisingly observed that, advantageously, when the

composition comprises one or more acids, the pH of the composition remains

WO wo 2021/024189 PCT/IB2020/057377

substantially constant over time, also for long periods, and the composition results to

be particularly stable, both physically and chemically.

In embodiments, the process of the invention can comprise a step of micronizing the

composition. As mentioned above, the step of micronizing the composition allows to

reduce the particle size of prothioconazole and optionally, of chlorothalonil within the

composition, to an average size (i.e. average diameter) which can be, for example,

between 1 um and 10 um.

Micronization is a process per se known and can be carried out by means of known

techniques. For example, the micronization of aqueous compositions, in particular of

aqueous suspensions preferably concentrated, can be carried out by using a wet pan

mill, e.g. the Dyno Mill wet pan mill with micro-balls.

In embodiments, the process of the invention can further comprise one or more steps

of adding one or more antifreezes, and/or one or more dispersants, and/or one or more

defoamers, and/or one or more biocide agents, and/or one or more thickeners.

Still object of the present invention is the use of a composition according to the

invention in the treatment and/or the prevention of fungal infections in plants.

Advantageously, the composition of the present invention can be produced in

concentrated form, e.g. in form of aqueous suspension concentrate (SC), and can be

diluted with water at the moment of its application to the plant.

For example, the composition of the invention can be diluted in water, obtaining a

diluted composition wherein the composition of the invention is in an amount in the

range between 0.05 wt% and 10 wt%, preferably between 0.1 wt% and 7 wt%, more

preferably between 0.15 wt% and 5 wt% relative to the total weight of the diluted

composition. For example, the composition of the invention can be diluted in water,

obtaining a diluted composition wherein the composition of the invention is in an

amount in the range between 0.2 wt% and 4.25 wt%, relative to the total weight of the

diluted composition.

The composition of the invention, properly diluted, can be provided to the plants

according to per se known techniques in the agrochemical field. For example, the

composition according to the invention, optionally diluted, can be provided to the

plants or to one or more parts thereof, by means of known spraying techniques.

WO wo 2021/024189 PCT/IB2020/057377

As mentioned above, the composition of the invention has several advantages with

respect to the compositions known in the art.

In particular, the composition of the invention has high physical and chemical stability.

For this reason, the composition of the invention can be stored and conserved, also for

long periods, without substantially undergoing physical and/or chemical alterations

which compromise the application and/or the effectiveness in the treatment and

prevention of fungal infections.

Moreover, the composition of the invention can comprise, in addition to

prothioconazole, at least one second active ingredient with antifungal activity, i.e.

chlorothalonil. In this case, the composition results to be particularly effective in the

treatment and/or the prevention of fungal infections in plants.

The invention will be described in more detail in the following Experimental Section,

by way of example only and without limitation.

Experimental Section

Example 1A - Preparation of compositions comprising prothioconazole and

chlorothalonil

Eight different compositions in the form of aqueous suspension concentrates (SC) have

been prepared by means of the process steps hereinafter described:

a) To a suitable amount of water, preferably under stirring, an antifreeze

(MPG), the surfactants present (Morwet® D-425; Ultrazine Na; Soprophor®

3D33), an aliquot of defoamer (Defomex 1510) and the optional amount of

intended acid are added; the different components are mixed by using a high

shear mixer, e.g. an Ultra Turrax mixer, until obtaining an homogeneous

mixture;

b) The active ingredients (prothioconazole and chlorothalonil), preferably

one at time, are added; after the addition of each active ingredient mixing is

performed until obtaining an homogeneous suspension, by using a high shear

mixer, such as Ultra Turrax;

c) the obtained suspension is micronized by means of a wet pan mill, e.g.

a Dyno® Mill with micro-balls; d) to the micronized suspension a thickener (Rhodopol® 23, previously dispersed in water at 2.7% to form a pregel), an antibacterial (Proxel® GXL) and the remaining amount of defoamer (Defomex 1510) are added.

Optionally, additional water can be added in order to obtain a composition having the

desired concentration of the different components.

In Table 1A, hereinafter reported, are set forth in detail the components and their

amounts (expressed as weight/weight percentages relative to the total weight of the

composition) in the different compositions obtained according to the just described

process.

TABLE 1A 1 2 3 4 5 6 7 8 COMPOSITIONS COMPONENTS (% W/W) % % % % % % % % Chlorothalonil (98% purity) 28.80 28.80 28.80 28.80 28.80 28.80 28.80 28.80

Prothioconazole (98.1% purity) 12.33 12.33 12.33 12.33 12.33 12.33 12.33 12.33

Morwet D-425 4.00 4.00 4.00 4.00 4.00 - - 4.00

Ultrazine Na 2.00 2.00 2.00 2.00 2.00 - - 2.00

Soprophor 3D33 - - - - - 3.50 3.50 3.50

5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 MPG 1M Sulfuric acid 1.50 1.50 - - - - - -

Citric acid 2.00 - - - - - - -

Phosphoric acid (50% sol.) 0.75 - - - - - -- -

Hydrochloric acid (50% sol.) 0.50 - - - - - - -

Defomex 1510 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

Proxel GXL 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

Rhodopol 23 2.7% 6.50 10.00 7.00 7.00 7.00 8.00 8.00 5.00

Water 41.17 36.17 38.67 39.92 40.17 42.17 40.67 39.17

total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

The raw materials used for the production of the tested compositions are per se known

and commercially available.

The purity degree indicated for prothioconazole and chlorothalonil raw materials are,

per se, not limiting for the purposes of the present invention. Moreover, it is known that, in commercial products, a certain fluctuation of such parameter is allowed and acceptable.

The product having the trade name "Morwet D-425" (AkzoNobel) is an anionic

surfactant belonging to the class of alkylnaphthalenesulfonates (in particular

methylnaphthalenesulfonate sodium salt), and it is commercially available.

The product having the trade name "Ultrazine Na" (Borregaard Lignotech) is an

anionic surfactant belonging to the class of lignosulfonates (in particular

lignosulfonates sodium salt), and it is commercially available.

The product having the trade name "Soprophor 3D33" (Solvay) is an anionic

surfactant, specifically a polyarylphenyl ether phosphate, and it is commercially

available.

"MPG" is monopropylene glycol, antifreeze commercially available.

The product having the trade name "Defomex 1510" (Lamberti) is a silicone defoamer,

and it is commercially available.

The product having the trade name "Proxel® GXL" (Lonza) belongs to the class of

benzisothiazolinones (in particular 1,2-benzisothiazolin-3-one), it is used as an

antibacterial and is commercially available.

The product having the trade name "Rhodopol® 23" (Solvay) is a xanthan gum-based

thickener, and it is commercially available.

Example 1B - Preparation of compositions comprising prothioconazole

Two compositions (compositions 9 and 10) in the form of aqueous suspension

concentrates (SC) have been prepared by means of the process steps described in

Example 1A. In this case the compositions do not include chlorothalonil.

In Table 1B, hereinafter reported, are set forth in detail the components and their

amount (expressed as weight/weight percentages relative to the total weight of the

process.

TABLE 1B COMPOSITIONS 9 10

COMPONENTS (% W/W) % % Prothioconazole (98.1% purity) 35.1 35.2

Soprophor 4D384 1.00 1.00

Morwet D-425 4.00 4.00

Ultrazine Na 2.00 2.00

5.00 5.00 MPG 1M Sulfuric acid 1.50 -

Citric acid 1.50 -

Defomex 1510 0.10 0.10

Proxel GXL 0.10 0.10

Rhodopol 23 2.7% 9.00 9.00

Water 42.2 42.1

total 100.00 100.00

The raw materials used for the production of the compositions are per se known and

are commercially available, as described above.

The product with the trade name "Soprophor 4D384" (Solvay) is an anionic

surfactant belonging to the class of alkylarylsulfonates, specifically a tristyrylphenol

sulfate (in particular, poly(oxy-1,2-ethanediyl),a-sulfo-w-2 4, 6-tris(1-

phenylethyl)phenoxy], ammonium salt) and it is commercially available.

Example 2 - evaluation of initial parameters

For each composition obtained according to Example 1A, the following parameters

are evaluated:

- pH - appearance (under microscope)

- residue 100 mesh (%)

- I residue 325 mesh (%)

viscosity (cPs). -

The pH of the compositions is measured according to per se known techniques, e.g. by

using a suitably calibrated pH meter, to measure the pH of the different non-diluted

compositions. In particular, the pH of the compositions of the invention has been

measured according to the CIPAC MT 75.3 method.

WO wo 2021/024189 PCT/IB2020/057377

The evaluation of the appearance under the optical microscope allows to observe the

crystals, i.e. the prothioconazole and chlorothalonil particles present in the

composition, and to visually evaluate their form, size and morphology.

The residue at 100 mesh and 350 mesh (expressed as % of the product which is retained

by the mesh of the sieve, with respect to the total amount of analyzed product) can be

determined according to the CIPAC MT 185 method.

The viscosity of the compositions is measured at the temperature of 25°C by using a

Brookfield model LVT viscometer according to the CIPAC MT 192 method.

The obtained results are set forth in Table 2A, hereinafter reported:

TABLE 2A 1 2 3 7 ANALYTICAL DATA 2 3 4 5 6 7 8

t=0

6.94 2.9 2.5 2.5 2.6 2.34 1.26 4.2 pH Microscope* regula regula regula regula regula regula regula regula

r rr r r r rr rr r

Residue 100 mesh (%) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

Residue 325 mesh (%) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Viscosity (cPs) 2130 2000 2050 2000 2250 1550 1450 2025

NOTES: *: a regular appearance under the microscope indicates a product wherein the crystals are well

separated and all substantially with the same form and size.

For each composition obtained according to Example 1B, the following parameters are

evaluated:

- Macroscopic appearance

viscosity (cPs) -

- pH - appearance (under microscope)

- residue 100 mesh (%)

- residue 325 mesh (%)

- suspensibility 1% (%)

- prothioconazole titre (%)

- laser 50% (um)

- - laser 90% (um)

- density (g/mL)

The macroscopic appearance of the compositions is evaluated by naked eye, evaluating

the possible presence of clear alterations such as, for example, phase separations or

sedimentations.

The viscosity, pH, and appearance under the microscope, residue at 100 mesh and 325

mesh, are analyzed as described above.

The parameter defined as "suspensibility 1%" can be determined according to the

official CIPAC MT 184 method. In this case, the composition is diluted to 1 wt% with

water and kept in a thermostated bath at 20°C for 30 minutes. The supernatant is

removed by suction and the residue on the bottom of the container is dried and

weighted. The results obtained indicate the wt% of initial composition which remains

in the suspension after dilution. For example, the composition 9 is diluted with water,

obtaining a diluted composition wherein the composition 9 is present in an amount of

1 wt% relative to the total weight of the diluted composition. Of this 1%, 95 wt%

remains in the suspension after dilution. The parameter "suspensibility 1%" provides

information concerning the behavior of the product under dilution. A good

suspensibility assures that no product accumulations are present on the bottom of the

barrel and that the distribution on the crops is homogeneous.

The prothioconazole titre, expressed as wt% relative to the total weight of the analyzed

composition, indicates the actual amount of such compound within the analyzed

sample. The prothioconazole titre can be determined by means of per se known

methods, e.g. by high-performance chromatography methods.

In particular, the prothioconazole titre can be determined by HPLC.

The parameters indicated as "laser 50%" and "laser 90%" can be measured by passing

a laser beam through a sample of the composition to be analyzed, forming a diffraction

pattern as a function of the size of the particles contained in the sample, and by

providing information on the Gaussian distribution of the particles size in the

suspension. The particle size distribution can be measured by using an infrared light

Malvern Mastersizer. By means of this instrument the volumetric distribution of the

particles in the suspension and the average diameters of the particle fractions

WO wo 2021/024189 PCT/IB2020/057377 PCT/IB2020/057377

corresponding to 50% and 90% of the total volume of the particles, are determined. In

particular, the compositions of the invention have been analyzed according to the

CIPAC MT 187 method.

The density is measured according to per se known techniques. The density of the

compositions can be measured by using a DMA 100M densimeter (Mettler Toledo).

The determination is usually carried out in a thermostated cell at 20°C. In particular,

the density of the compositions of the invention has been measured according to the

EEC A.3. method.

The obtained results are set forth in Table 2B, hereinafter reported:

TABLE 2B ANALYTICAL DATA t=0 9 10

Macroscopic Appearance* regular regular

Viscosity (cPs) 2000 1960

3.0 2.74 pH Microscope** regular regular

Residue 100 mesh (%) 0.01 0.01

Residue 325 mesh (%) 0.1 0.1

Suspensibility 1% (%) 95 94 Prothioconazole titre (%) 35.7 36

Laser 50% (um) 1.9 2.3

Laser 90% (um) 5.04 6.2

Density (g/mL) 1,151 1,155

NOTES: *: with "regular" macroscopic appearance it is meant a product in which the mass is fluid and

homogeneous without superficial separations or sedimentations.

** : a regular aspect under the microscope indicates a product in which the crystals are well separated

and all with substantially the same form and size.

In particular, from the results set forth in Tables 2A and 2B, it is possible to observe

that all the compositions have a pH <7. In particular, the compositions 2, 3, 4 and 5,

each comprising two sulfonate surfactants and one inorganic or organic acid, have a

pH between 2.5 and 2.9.

WO wo 2021/024189 PCT/IB2020/057377

Moreover, all the compositions have a residue 100 mesh of 0.01% and a residue 325

mesh of 0.1%.

Example 3 - evaluation of parameters after storing at room temperature for 14 days

The products obtained according to the process described above and having the

compositions according to Table 1A have been stored for 14 days at room temperature

and their following parameters have been evaluated:

- Macroscopic appearance

viscosity (cPs) -

- pH - appearance (under microscope)

- residue 100 mesh (%)

- residue 325 mesh (%)

- suspensibility 1% (%)

- prothioconazole titre (%)

chlorothalonil titre (%) -

- laser 50% (um)

- laser 90% (um)

- density (g/mL)

sedimentations.

The viscosity, pH, and appearance under the microscope, residue at 100 mesh and at

325 mesh, are analyzed as described in Example 2.

The parameter defined as "suspensibility 1%" can be determined according to the

removed by suction and the residue on the bottom of the container is dried and

in the suspension after dilution. For example, the composition 1 is diluted with water,

obtaining a diluted composition wherein the composition 1 is present in an amount of

1 wt% relative to the total weight of the diluted composition. Of this 1%, 92 wt%

WO wo 2021/024189 PCT/IB2020/057377

information concerning the behavior of the product under dilution. A good

barrel and that the distribution on the crops is homogeneous.

The prothioconazole titre and the chlorothalonil titre, which are expressed as wt%

relative to the total weight of the analyzed composition, indicate the actual amount of

such compounds within the analyzed sample. The prothioconazole and chlorothalonil

titres can be determined by means of per se known methods, e.g. by high-performance

chromatography methods.

In particular, the chlorothalonil titre has been determined according to the CIPAC

288/SC/M/2, CIPAC Handbook K method.

The prothioconazole titre can be determined by HPLC.

providing information on the Gaussian distribution of the particles size in the

particles in the suspension and the average diameters of the particle fractions

CIPAC MT 187 method.

compositions can be measured by using a DMA 100M densimeter (Mettler Toledo).

EEC A.3. method.

The obtained results are set forth in Table 3A, hereinafter:

TABLE 3A ANALYTICAL DATA AFTER 14 DAY AMBIENT 1 2 3 4 5 6 7 7 8

Macroscopic regula regula regula regula regula regula non- non-

Appearance* r r r r r regular regular r

Viscosity (cPs) 1990 1810 2020 1910 2080 1320 1105 1810

4.9 2.7 2.3 2.4 2.3 2 1.4 3.3 pH Microscope** regula regula regula regula regula regular regular regula

r r r r r r

Residue 100 mesh 0.01 0.01 0.01 0.01 0.01 -- -- --

(%)

Residue 325 mesh 0.1 0.1 0.1 0.1 0.1 - - -

(%)

Suspensibility 1% 92 94 97 92 94 -- -- --

(%)

Prothioconazole 12.3 12.3 12.5 12.3 12.3 12.2 12.6 11.5

titre (%)

Chlorothalonil 28.4 28.4 28.6 28.5 28.2 28.5 28.5 28.3

titre (%)

Laser 50% (um) 1.36 1.71 1.73 1.77 1.48 -- -- --

Laser 90% (um) 4.21 4.99 5.17 5.28 4.43 -- -- --

Density (g/mL) 1,237 1,236 1,242 1,235 1,237 -- -- --

homogeneous without surface separations or sedimentations; on the contrary, where a "not regular

"appearance is indicated, it is meant a product which is gelled and/or inhomogeneous and/or having

surface separation.

* : a "regular" appearance under the microscope indicates a product in which no crystal growth

phenomena meant as variation of the crystal morphology and/or formation of agglomerates with

respect to the measurements at time 0 are observed.

As can be observed from Table 3A, after 14 days at room temperature, the

compositions 6 and 7, wherein no sulfonate surfactant is present, have a non-regular

appearance. In particular, such compositions had an inhomogeneous, gelatinous

appearance, and phase separation.

WO wo 2021/024189 PCT/IB2020/057377

On the contrary, the compositions 1-5 and 8, after 14 days of storage at room

temperature, retain a regular appearance, in particular homogeneous and without phase

separations, substantially unchanged with respect to that found at time 0 (non-

specifically set forth in Table 2A).

Example 4 - evaluation of parameters after storing at 54°C for 14 days

The products obtained according to the above described process and having the

compositions according to Table 1A and Table 1B, have been stored for 14 days at

54°C, this way simulating the behavior of the product during its shelf life, i.e. after

two years of storage at room temperature.

In particular the following parameters have been evaluated:

- Macroscopic appearance

viscosity (cPs) -

- pH - appearance (under microscope)

- residue 100 mesh (%)

- residue 325 mesh (%)

- suspensibility 1% (%)

prothioconazole titre (%) -

- prothioconazole degradation (%)

chlorothalonil titre (%) -

- laser 50% (um)

- laser 90% (um)

The prothioconazole degradation can be determined by HPLC.

The other parameters considered have been evaluated as described above.

TABLE 4A ANALYTICAL DATA AFTER 14 DAYS +54°C 1 2 3 4 5 6 7 8

Macroscopic regul regul regul regul non- non- non- non-

appearance regular ar ar regular regular regular ar ar

Viscosity (cPs) 5440 1780 1980 1980 1920 2090 11400 11400 15150 15150 1025

2.7 2.6 2.3 2.3 2.2 1 1.2 1.5 pH

TABLE 4A ANALYTICAL ANALYTICAL DATA DATA AFTER AFTER 14 14 DAYS DAYS +54°C +54°C 1 2 2 3 4 4 5 6 6 7 7 8 8

Microscope** regul regul regul regul non- non- non- non-

regular ar ar ar regular regular regular ar ar ar ar

Residue 100 mesh 0.02 0.01 0.02 0.02 0.02 - - --

(%)

Residue 325 mesh 0.4 0.4 0.2 0.1 0.1 0.1 - -- --

(%) Suspensibility 73 94 94 94 90 90 94 1% -- -- --

(%)

Prothioconazole titre 11.8 12.2 12.5 12.3 11.9 11.3 11.7 11.4

(%)

Prothioconazole Prothioconazole 4.06 0.8 0 0 0 0 3.25 7.4 7.14 0.9

degradation (%)

Chlorothalonil titre 28.1 28.3 28.6 28.5 27.8 28.2 28.3 28.3

(%)

Laser 50% (um) 3.2 1.54 1.69 1.75 1.37 -- -- --

Laser 90% (um) 17.3 4.68 5.11 5.26 4.23 - - --

surface separation.

** : a "regular" appearance under the microscope indicates a product in which no crystal growth

respect to the measurements at time 0 are observed.

TABLE 4B ANALYTICAL DATA AFTER 14 DAYS +54°C 9 10

Macroscopic appearance* regular regular

Viscosity (cPs) 1825 2050 2.9 2.6 pH Microscope** regular regular

Residue 100 mesh (%) 0.01 0.01

WO wo 2021/024189 PCT/IB2020/057377 PCT/IB2020/057377

Residue 325 mesh (%) 0.1 0.1

Suspensibility 1% (%) 92 92 Prothioconazole titre (%) 35.7 35.5

Prothioconazole degradation (%) 0 1.4

Laser 50% (um) 2.09 3.6

Laser 90% (um) 5.53 6

homogeneous without superficial separations or sedimentations.

a "regular" appearance under the microscope indicates a product in which no crystal growth

respect to the measurements at time 0 are observed.

As can be observed from Table 4A, the compositions 2-5 including at least one organic

or inorganic acid and at least one sulfonate surfactant (in this case two sulfonate

surfactants) show a good physical stability after storing at 54°C for 14 days. Indeed,

for such compositions the viscosity found at time 0 remains substantially unchanged,

and neither crystal growth nor sedimentation or any phase separation is observed.

The same compositions 2-5 show chemical stability as well after storage at 54°C for

14 days. Indeed, such compositions have a degradation level of prothioconazole

between 0% and 3.25%, which results to be acceptable because lower than the

threshold value of 5% set forth by FAO Manual (first edition, third revision of 2016)

and which does not compromise the applicability and fungicide effectiveness of the

composition.

Analogously, as can be seen from Table 4B, the compositions 9, 10, which include at

least one organic or inorganic acid and at least one sulfonate surfactant (in this case

three sulfonate surfactants) show a good physical stability after storage at 54°C for 14

days. Indeed, also in these cases neither crystal growth, nor sedimentation or phase

separation is observed.

The same compositions 9 and 10 show chemical stability as well after storage at 54°C

for 14 days. Indeed, such compositions have a degradation level of prothioconazole

between 0% and 1.4%, which results to be acceptable because lower than the threshold value of 5% set forth by FAO Manual (first edition, third revision of 2016) and which does not compromise the applicability and fungicide effectiveness of the composition.

Claims

CLAIMS 1. An aqueous composition comprising prothioconazole, optionally chlorothalonil, and at least one sulfonate surfactant, said composition having a pH ≤5, further comprising at least one acid selected from inorganic acids, organic acids and 5 mixtures thereof, wherein said at least one acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, citric acid and mixtures thereof. 2020325766
2. The composition according to claim 1, wherein said composition has a pH ≤3.5, preferably comprised between 2 and 3.5.
3. The composition according to claim 1 or 2, wherein said pH of the composition 10 has a variation that remains within one pH unit, preferably 0.5 pH units, over time.
4. The composition according to any one of the preceding claims wherein said at least one sulfonate surfactant is selected from alkylsulfonates, alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids, sulfonates of alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of 15 condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates, sulfosuccinamates and mixtures thereof, preferably from alkylnaphthalenesulfonates, lignosulfonates and mixtures thereof.
5. The composition according to any one of the preceding claims, wherein said 20 composition comprises at least one alkylnaphthalenesulfonate surfactant and at least one lignosulfonate surfactant, preferably at least one methylnaphthalenesulfonate surfactant and at least one lignosulfonate surfactant, and optionally one alkylarylsulfonate surfactant.
6. The composition according to any one of the preceding claims, wherein the 25 amount by weight of said prothioconazole is between 1% and 50%, preferably between 2% and 45%, more preferably between 2% and 40%.
7. The composition according to any one of the preceding claims, wherein the amount by weight of said chlorothalonil is between 1% and 55%, preferably between 10% and 55%, more preferably between 20% and 55%.
8. The composition according to any one of the preceding claims, wherein the amount by weight of said at least one sulfonate surfactant is between 0.5% and 25%, preferably between 2% and 15%, more preferably between 4% and 10%.
9. The composition according to any one of the preceding claims, wherein the 5 concentration of said prothioconazole is between 10 g/l and 600 g/l, preferably between 20 g/l and 500 g/l, more preferably between 30 g/l and 450 g/l. 2020325766
10. The composition according to any one of the preceding claims, wherein the concentration of said chlorothalonil is between 100 g/l and 700 g/l, preferably between 200 g/l and 700 g/l, more preferably between 300 g/l and 700 g/l. 10
11. The composition according to any one of the preceding claims, said composition being an aqueous suspension concentrate (SC).
12. The composition according to any one of the preceding claims, further comprising one or more antifreezes, and/or one or more dispersants, and/or one or more defoamers, and/or one or more biocide agents, and/or one or more thickeners. 15
13. A process for the preparation of a composition according to any one of the preceding claims, comprising a step of mixing prothioconazole, optionally chlorothalonil, and at least one sulfonate surfactant, in water, and further comprising a step of adding at least one acid selected from inorganic acids, organic acids and mixtures thereof, wherein said at least one acid is selected from sulfuric acid, 20 phosphoric acid, hydrochloric acid, citric acid and mixtures thereof.
14. The process according to claim 13, further comprising a step of micronizing said composition.
15. Use of a composition according to any one of claims 1 to 12 in the treatment and/or in the prevention of fungal infections in plants.